Metal–organic frameworks (MOFs) are porous crystalline materials constructed from metal ions or clusters and multidentate organic ligands. Recently, the use of MOFs or MOF composites as catalysts for synergistic catalysis and tandem reactions has attracted increasing attention due to their tunable open metal centres, functional organic linkers, and active guest species in their pores. In this review, the applications of MOFs with multiple active sites in synergistic organic catalysis, photocatalysis and tandem reactions are discussed. These multifunctional MOFs can be categorized by the type of active centre as follows: (i) open metal centres and functional organic linkers in the MOF structure, (ii) active guest sites in the pores and active sites in the MOF structure, and (iii) bimetallic nanoparticles (NPs) on MOF supports. The types of synergistic catalysis and tandem reactions promoted by multifunctional MOFs and their proposed mechanisms are presented in detail. Here, catalytic MOFs with a single type of active site and MOFs that only serve as supports to enhance substrate adsorption are not discussed.

Multifunctional metal–organic framework catalysts: synergistic catalysis and tandem reactions

Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

Emerging Multifunctional Metal-Organic Framework Materials.

Metal organic frameworks (MOFs) are a class of porous crystalline materials that feature a series of unique properties, such as large surface area and porosity, high content of transition metals, and possibility to be designed and modified after synthesis, that make these solids especially suitable as heterogeneous catalysts. The active sites can be coordinatively unsaturated metal ions, substituents at the organic linkers or guest species located inside the pores. The defects on the structure also create these open sites. The present review summarizes the current state of the art in the use of MOFs as solid catalysts according to the type of site, making special emphasis on the more recent strategies to increase the population of these active sites and tuning their activity, either by adapting the synthesis conditions or by post-synthetic modification. This review highlights those reports illustrating the synergy derived from the presence of more than one of these types of sites, leading to activation of a substrate by more than one site or to the simultaneous activation of different substrates by complementary sites. This synergy is frequently the main reason for the higher catalytic activity of MOFs compared to homogeneous catalysts or other alternative solid materials. Besides dark reactions, this review also summarizes the use of MOFs as photocatalysts emphasizing the uniqueness of these materials regarding adaptation of the linkers as light absorbers and metal exchange at the nodes to enhance photoinduced electron transfer, in comparison with conventional inorganic photocatalysts. This versatility and flexibility that is offered by MOFs to optimize their visible light photocatalytic activity explains the current interest in exploiting these materials for novel photocatalytic reactions, including hydrogen evolution and photocatalytic CO2 reduction.

Catalysis and photocatalysis by metal organic frameworks

Metal–organic frameworks (MOFs) are crystalline porous materials formed from bi- or multipodal organic linkers and transition-metal nodes. Some MOFs have high structural stability, combined with large flexibility in design and post-synthetic modification. MOFs can be photoresponsive through light absorption by the organic linker or the metal oxide nodes. Photoexcitation of the light absorbing units in MOFs often generates a ligand-to-metal charge-separation state that can result in photocatalytic activity. In this Review we discuss the advantages and uniqueness that MOFs offer in photocatalysis. We present the best practices to determine photocatalytic activity in MOFs and for the deposition of co-catalysts. In particular we give examples showing the photocatalytic activity of MOFs in H2 evolution, CO2 reduction, photooxygenation, and photoreduction.

Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production.

Metal-organic frameworks (MOFs), a new class of crystalline porous organic-inorganic hybrid materials, have recently attracted increasing interest in the field of energy storage and conversion. Herein, recent progress of MOFs and MOF composites for energy storage and conversion applications, including photochemical and electrochemical fuel production (hydrogen production and CO2 reduction), water oxidation, supercapacitors, and Li-based batteries (Li-ion, Li-S, and Li-O2 batteries), is summarized. Typical development strategies (e.g., incorporation of active components, design of smart morphologies, and judicious selection of organic linkers and metal nodes) of MOFs and MOF composites for particular energy storage and conversion applications are highlighted. A broad overview of recent progress is provided, which will hopefully promote the future development of MOFs and MOF composites for advanced energy storage and conversion applications.

Pristine Metal–Organic Frameworks and their Composites for Energy Storage and Conversion

A dye-sensitized Pt@UiO-66(Zr) metal–organic framework for visible-light photocatalytic hydrogen production

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A dye-sensitized Pt@UiO-66(Zr) metal–organic framework for visible-light photocatalytic hydrogen production